Photochemical production of benzene hexachloride



0 1953 A. MILLER ET AL PHOTOCHEMICAL PRODUCTION OF BENZEINE HEXACHLORIDE Filed May 10 1949 3 Sheets-Sheet l N 9 2 Lu I D 2 v LL {A a l J E l w m I N u.! G: D 2 I J l &'l

N h C.

KN) N J J N J N l J J J lJ J \J 6; J '2 INVENTORS JAMES H. DUNN LEO A. MILLER 8 BY CLARENCE M. NEHER Oct. 20, 1953 A. MILLER ET AL PHOTOCHEMICAL PRODUCTION OF BENZENE HEXACHLORIDEI 3 Sheets-Sheet 2 Filed May 10, 1949 INVENTORS JAMES H. DUNN LEO A. MILLER BY CLARENCE M. NEHER Oct. 20, 1953 L. A. MILLER ET AL 6,3 3

PHOTOCHEMICAL PRODUCTION OF BENZENE HEXACHLORIDE Filed May 10, 1949 3 Sheets-Sheet 3 FIGURE 4 lLl LI-l 0.000s gm 1 1: LI-l 1 40 6O TEMPERATURE, DEGREES C FIGURE 5 INVENTORS JAMES H. DUNN LEO A. MILLER BY CLARENCE M. NEHER Patented Oct. 20, 1953 PHOTOCHEMICAL PRODUCTION OF BENZENE HEXAGHLORIDE Leo A. Miller, James H. Dunn, and Clarence M.

Neher, Baton Rouge, La., assignors to Ethyl Corporation, New York, N. Y., a corporation of Delaware Application May 10, 1949, Serial No. 92,266

1 Claim.

This invention relates to the manufacture of chlorinated hydrocarbons and apparatus for the manufacture thereof. In particular, the invention is concerned with the manufacture of benzene hexachloride and a new and improved method of carrying out the formation reaction.

Benzene hexachloride, CsHeClc, also called hexachlorocyclohexane or Gammexane, is an important industrial chemical. Its insecticidal potency, particularly of the gamma isomer, is well known. It has been known for a long period that benzene hexachloride could be produced by the complete addition chlorination of benzene. However, no fully satisfactory method has as yet been disclosed for this reaction.

An object of the present invention is to provide a new and improved reaction technique. An additional object is to overcome some of the specific deficiencies of the prior art. A further object is to provide an efficient continuous process and apparatus for carrying out the process. A still further object is to provide a higher degree of conversion of benzene to benzene hexachloride.

The principal reaction method of the prior art involves the batchwise photochemical chlorination of benzene in a reaction pot or vessel. The chlorination is continued until the quantity of benzene hexachloride produced is sufiicient to exceed the solubility in benzene, and a large proportion of benzene hexachloride formed is present in the solid phase. Chlorination is then stopped and the mixture of unreacted benzene, dissolved benzene hexachloride, and solid benzene hexachloride removed from the reactor. The solids are separated by filtration, the liquid or filtrate being then combined with fresh benzene and returned to the chlorination step.

The above reaction method, although it has been commercially used, is far from being entirely satisfactory. A particular disadvantage of the method is the physical condition of product mixture resulting. A mixture of solids and liquids is of course more difiicult to handle than a liquid system. In the manufacture of benzene hexachloride the disadvantage of a mixture of solids and liquids is even more pronounced. The crystals of benzene hexachloride tend to deposit in the equipment and to cause plugging of pumps, valves and lines. Thus, the reacted mixture is quite unsuitable for product separation and recovery. A further disadvantage of the prior art method is the frequent necessity of discarding large amounts of the reactor solution. This wasteful operationis necessitated because the recovery method is predicated upon the formation of a separate solid product in the reactor proper. The efiect of this technique is to cause a build up in concentration of any impurities in the reactor solution. These impurities may be normally liquid or normally solid materials resulting from the chlorination of impurities in the feed benzene. As the reaction technique contemplates a benzene hexachloride recovery operation such as filtration or the like, these impurities are ordinarily removed from the system by the obviously wasteful procedure of discarding the solution at periodic intervals. Alternatively, the benzene may be distilled off and the impurities separated. This has the disadvantage of introducing another step in the overall process.

An additional fault of the batchwise chlorination method described is the irregular concentration of the various isomers of the product. This is caused by the fact that the different isomers of benzene hexachloride have varying solubilities in benzene. Hence, in chlorinating until solids are formed, those first precipitated in the reactor do not correspond in proportions to the overall analysis of the benzene hexachloride actually formed by the reaction. This requires careful reblending of the products in order to offer a material of uniform composition.

In brief, the prior method of making benzene hexachloride suffers the disadvantages of producing a reaction mixture which is difiicult to handle and process further. In addition, the technique employed requires frequent discard of valuable materials, or else a separate recovery operation to isolate unreacted benzene after interruption of the reaction. The batchwise chlorination also necessitates reblending of the final solid produced to obtain a uniform product.

It is an object of our invention to avoid serious difficulties of the prior art. In addition, our reaction fully meets the other objective of providing a continuous and highly efificient method giving a high yield of benzene hexachloride.

These objectives are attained by controlling the proportions of chlorine and benzene present so that the existence or formation of benzene hexachloride in the solid phase is avoided. In addition, we irradiate the reaction mixture for a relatively extended period while confining the mixture as a stream of limited cross sectional area. These concurrent requirements are essential to the accomplishment of the objectives of our reaction method.

In order to avoid the formation of a solid phase in the reactor, the proportion of chlorine sists in determining the chlorinezbenzene ratio 1 r at which solid benzene-hexachloride is first formed, and then reducing the chlorine rate a .10 a t o h slight quantity below that value. In practice, I

this can be done by operating at a specific chl'o rinezbenzene ratio until a. steady state is reached, then raising :the chlorine: flow. slightly. [$118 reaction mixtureds-observed c1ose1y.and the cycle is .repeated .untilv solids .are formed. chlo- :rinezbenzene ratio ;then immedia ely reduc d :to prevent further .formation of .solidzbenzene hexachloride.

A: preferredmethod of controlling the reaction employs ..density.of .the reaction solution as a control variable. Itihaszbeencfound that the density of the solution at the. limitingcondition, when correctedto 220 C. bears. a ,linear relationship to zthe solutionitemperature. e'I-hislimiting relationship .is .expressed as .where d.-.-.density at 120 rams :per cubi .:centimeter, .and T.- the solution temp ratur hedens ty. d. t e cont o variabl i de r in d on niently b mea u em nt i -t e a t 9 vtiqn dens ty wit .a' ydro e a a y c n e e "ie'nt temperature. observed density is the? corre t d to t d ns ty a 20C- n in e rated av a e den t or t n f r i s n b i ed- "f h actual d n r e rred c ndit s s. Irene "10 t "1-03 ra P r pub centimeter.

t hasibeen'i un hei'th m n den i expresse'd by-the equation given above, does-not e poi i i th y' i satur ted olu o of -benzene hexachloride. "Rather, this limiting i i' t a fini am u t b w hat c rre pondmg to saturation. The 'reasonfor'this difference f not :fully understood, as-it -niight be expected that it wouldbe possible-to chlorinate-upto the saturation limit for thesolution. -9ne--possible explanation "might be the existence of {a slow moving film of solution at the cooled walls A of a reactor. 'Precipitation of -benzene hexach-lor-ide crystals would probably occur because of the lower -temperature at that point. By nraintaini'ng the solution density as--specified'-above, such difficulty is *avoided. order to operate below the-defined density limitation-weemploy a 'relatively low chlorine-to benzene feed ratio. 'The density-is controlled by varying this ratio. is contrast to prior methods, --which taught 1 that A chlorination --should be carried-to asgreat'aneextent as'possi-ble. In actualoperation,thedetermination of the den- -sityof the reaction mixture at only onepoint is usually adequate. 'Preferably, we measure the density of the reacted mixture =leaving -the re- :actor. I

fihe :entire reacting mixture is exposed to eetinic light for an extended period. A reaction period of five minutes or more is ordinarily required in our operation, a preferred reaction period being about 15 minutes. In almost every case, a reaction period of 20 minutes is adequate for relatively complete conversion of chlorine to benzene hexachloride.

It will be noted that our method insures that every portion of the reacting mixture is irradiatediorthe inll extended period described above. This assures uniform conversion of the chlorine in its passage through the reactor. In prior :methodsstratification of the reaction mixture permits discharge :of unreacted chlorine. Our -methodavoids this difficulty and assures that the chlorine-is-retained in the radiation zone for the :isl series r-iwl Additional requirements of our reaction method are the steps of maintaining the reaction mixture as a stream of limited cross sectional area and comp etely ir ad a m thi stream wi :actinic li :Bsr ompletelwirradiat n wo ferto transmission .0, a ini lieh zthr u entire cross section 10f i fi :st eam- 'Elfl 34 f a stream f relatively li i ed c iqs sect ona makes,possiblerthisecomp fi i irra iat nther advantage of ailimited .crosssect onal a; is theavoidance of :stratification, so that them,- action :mixture is uniform at any .z l 7m}? section. Our reaction,streammaybe-maintained n c a lar. square..circu1ar,- or nnular cross section. Other irregular crossasectionszar quit suitable. We have :found :that, with who Pile.- ferrecl light sources, the cross:section-shouldordi: narily have a hydraulic-radius not in excess of1l.5 inches. This figure is ,notgliowevenen:absolll limitation, .as .even larger streams can be 1-..11tilized when an especially intense :actinic light source is available. ,Apreferred sizeof reaction stream, particularly suited for use with currently available actinic light .sources, is a streaan with a hydraulic radiusof 0fl5s'inch. "Smallerstreams are satisfactory, but as .a practical (matter, -,we have found it preferable not to go below astream .with a hydraulic radius of 0.5 :inch.

A variety of embodiments of our tinvention is possible, providing :that s t-he limitations hereto.- fore stated are adhered-to. The accompanying figures illustrate several embodimentsand-.means of carrying out .the inv-ention. Figure i1 :is an elevation view of :a preferred embodiment .uti: lizing a reactor conduit of: highcapacity. #Figure 2 :shows a transverse section of a reactor icon-,- -duit along line 2+2/of'rFigure 1.as .well asmeans of supplying actinic light to the reaction mixture. Figure 3iillustrates=an embodimentecarrie'd out in a .more economically constructed sre'a'ctor. Figure 4 shows :a transverse section of the reac: tor of Figures along lines 54:4. LIB Figure a. density correction factorzis graphically-shown.

Referring to Figure .1, this embodiment.:em.- .ploys a reactor comprising ;an extended .nylinr drical' conduit transmissive .of actinic :light. zchlorine -.gas :is fed ito ithe .unitathrough zline ail]. :the flow being controlled :by ivalue 2H Aliquid stream predominatingin r benzene is 1 fed :through :line l2,-the rate of new being. controlled: byiva lve l3. The. chlorine andi benzine containingastream mix in linedidgthe chlorine dissolving: ine the.-ben.- .zene. The mixture then: immediately flows' to tlie reactor. The reactor is composed of .a -.-'series of :light transmissive :t'ubes I5 I connected -by return bands :15.

Ihereaction mixture is zsubjectedxtorthe action of act-inic 2 light-radiated by fluorescent lights it].

In passing through the conduit, the chlorine is completely converted to benzene hexachloride by reaction with the benzene.

The reacted mixture, comprising benzene and benzene hexachloride is discharged from the reactor through line I8 and flows to suitable re covery operations. The temperature of the reaction mixtures can be measured by several temperature indicators I9. Samples are withdrawn for measurement of density through sample connections 20. Density of the solution is quite simply adjusted by increasing or decreasing the chlorine feed rate while keeping the benzene rate constant.

The reaction of benzene and chlorine liberates appreciable quantities of heat which must be dissipated in part from the liquid phase. Cool ing water is fed to the unit through line 28 and valve 2|, to a distributing trough 22. Trough 22 is merely a V trough in which water flows over the edges 23 and drips from a notched distributor plate 24 which is aligned above the reaction tube I5.

. Figure 2 is a transverse sectional view 2-2 of the reaction conduit of Figure 1. In this embodiment the preferred light sources are tubular fluorescent lights I'I emitting white light varying from 4000 to 7000 Angstrom units. The preferred disposition of the lights is such that the cooling water 21 forms a continuous peripheral stream around the reaction conduit I5. The conduit I5 is filled or substantially filled with the reacting mixture in liquid phase 25 as indicated. A small amount of vapor 2B is formed, the quantity dependent on the temperature and possible substitution chlorination of impurities in the benzene, resulting in hydrogen chloride formation.

A second embodiment of our invention is shown by Figures 3 and 4. Figure 3 is a plan view of the reactor. The reactor of the present embodiment differs from the reactor of Figure 1 in that it is of unitary construction. The reactor is essentially a cast concrete slab 50 with a reaction channel 52 cast therein. Referring to Figure 4, a transverse section 4-4 of the reactor, the reaction conduit 52 is completed by a cover 5I of glass or other material transmissive of actinic light. The channels 52 in the concrete are 'preferably sealed with an impervious coating of carbon-phenolic resin cement or other impermeable material. The light transmissive cover 5| is preferably secured in place with a layer of impervious cement 54. The conduits 52 are preferably coated with a lining of impervious cement 53. Light sources are not shown by Figures 3 and 4. In this embodiment they are suspended above the light transmissive cover 5I by any convenient means.

The reaction in the present apparatus is carried out in much the same manner as in the reactor of Figure 1. Chlorine gas is fed through line 55 and valve 55 and admixed with a predominantly benzene solution fed through line 51 and valve 58. The mixture is fed to conduit 52 through line 59.

The reaction occurs as in the reactor of Figure 1, a certain amount of vaporization occurring. The present reactor is not as efficiently cooled as a reactor cooled around its entire periphery. However, as explained hereafter, temperature is not a critical factor in the reaction. Heat removal is accomplished by flow of cooling water 60 across the glass cover 5|, the water being supplied by pipe 65. For operation at high capacity, a cooling tube 64 can be built into the conduit 52.

The reacted mixture is discharged from the co duit 52 through line 6|, temperature being observed by indicator 62. Samples are removed by sample connection 63, for measurement of the density for control purposes.

The temperature at which we carry out the reaction is not critical although it is important. We have found that temperature has very little efiect on reaction rate, which is contrary to published information (Slator, Journal of the Chemical Society 83, p. 729 et seq). However, we have found that it is ordinarily preferable to maintain the solution temperature at not over 80 C.

Operating at a temperature above 80 C. necessi-.

It will be noted that the use of a reaction stream of restricted cross section, as utilized in our method, possesses the additional advantage that temperature is easily controlled.

The pressure of operation is not a limiting factor as the desired reaction'occurs in the liquid phase. For practical convenience, we have found that an operating pressure slightly above atmospheric is preferred. Operating pressures which are much higher than 15 pounds per square inch should not ordinarily be used, as they introduce numerous practical engineering problems. The preferred range is 5 to 15 pounds per square inch, dependent on the pressure drop at the operating rate.

The benzene feed stream may be pure benzene or may contain appreciable amounts of dissolved benzene hexachloride. The permissible use of a recycled dilute solution of benzene hexachloride is especially useful in continuous operations.

A basic requirement of our reaction method is that a relatively large proportion of benzene is fed. Hence, substantial amounts of benzene are recycled after removal of all or a part of the benzene hexachloride content of the outlet stream. The preferred composition of the henzene feed stream is less than 15 percent benzene hexachloride. It is ordinarily uneconomical and unnecessary for the benzene hexachloride content to be less than 2 percent benzene hexachloride.

The benzene hexachloride in the product solution from our reaction can be recovered in several ways known to the art. For example, steam distillation is a suitable method of separation. An especially advantageous method comprises vaporizing the benzene at relatively low temperature, and fusing the benzene hexachloride at a temperature of over C.

The reaction can be maintained by various types of actinic light. Sunlight, ultraviolet light, or the irradiation from a carbon are are suitable. The effectiveness of different types of light is attributed to the wide spread of spectral absorption by chlorine. Although various forms of actinic light thus can be used, we have found that a preferred light source is fluorescent tubular lights emitting white light. These light sources give forth light ranging between 4000 and 7000 Angstrom units. The preferred intensity of such light is that produced by wattage of from 10 to 20 per lineal foot of reaction conduit. 

